Realizing High Capacity and Zero Strain in Layered Oxide Cathodes via Lithium Dual-Site Substitution for Sodium-Ion Batteries

Sodium-ion batteries have garnered unprecedented attention as an electrochemical energy storage technology, but it remains challenging to design high-energy-density cathode materials with low structural strain during the dynamic (de)sodiation processes. Herein, we report a P2-layered lithium dual-site-substituted Na0.7Li0.03[Mg0.15Li0.07Mn0.75]O2 (NMLMO) cathode material, in which Li ions occupy both transition-metal (TM) and alkali-metal (AM) sites. The combination of theoretical calculations and experimental characterizations reveals that LiTM creates Na-O-Li electronic configurations to boost the capacity derived from the oxygen anionic redox, while LiAM serves as LiO6 prismatic pillars to stabilize the layered structure through suppressing the detrimental phase transitions. As a result, NMLMO delivers a high specific capacity of 266 mAh g-1 and simultaneously exhibits the nearly zero-strain characteristic within a wide voltage range of 1.5-4.6 V. Our findings highlight the effective way of dual-site substitution to break the capacity-stability trade-off in cathode materials for advanced rechargeable batteries.